Method for preventing the uncontrolled growth of microorganisms

ABSTRACT

The invention relates to a method for controlling biological processes, particularly digestion processes in water, particularly in stagnant or flowing water systems, whereby a certain quantity of tree resins is added to the water.

The invention relates to a method for controlling biological processes,particularly digestion processes in water, having the additionalfeatures of the preamble of patent claim 1.

Known from WO 01/88205 A1 is a method for producing sugar orsugar-containing products from sugar-containing vegetable raw materials,which method is carried out at least partially in the presence of addednatural, food-compatible resins. These food-compatible resins can betree resins, particularly colophony or colophony derivatives. These treeresins serve to inhibit specific microorganisms.

In both stagnant and flowing water systems, the danger of the growth ofmicroorganisms always exists, e.g. of bacteria, fungi, algae, and thelike, which growth leads to a considerable lowering of the waterquality. This is problematic, for example, in flowing water systems inthe food field, in which the water flow is used, for example, totransport the foods.

Chemical agents for avoiding the uncontrolled growth of microorganismsare known, which agents, however, are associated with serious negativesecondary effects. For the most part, such chemical substances are toxicfor humans and animals. Thus, natural substances possessing thenecessary antimicrobial characteristics are preferable.

The object of the present invention is to make available a method forcontrolling biological processes in water, which method isenvironmentally friendly, compatible with human health, simple to carryout, and cost-effective.

This object is achieved through the collective teaching of patent claims1 and 12. Advantageous further developments of the method in questionresult from the dependent claims 2-11 and 20-22, and, respectively,13-22.

An advantageous compound for controlling biological processes in wateris taught in patent claims 24-26 and 27-28.

In the method according to the invention for controlling biologicalprocesses, particularly digestion processes in water, particularly instanding and flowing water systems, a certain amount of tree resins isadded to the water. Tree resins can control the growth of microorganismsin water. In this context, the word “control” comprehends both thedestruction and removal of micro- and/or macroorganisms. The controllingof the biological processes takes place by means of the tree resins in apurely natural way. In addition, tree resins are quite storable, can beintegrated into the process without trouble, and are available insufficient amounts. The method according to the invention can be appliedin the most varied fields, e.g. in the food industry, e.g. in brewerypasteurization; air purifier systems; in the oil industry; fountains;water pipes, water tanks, wastewater systems, wastewater purification,etc.

With particular advantage, colophony and/or colophony derivatives can beused as tree resins. Precisely these resins have proved excellent andespecially advantageous in the method for controlling biologicalprocesses in water.

In order to ensure an effective control of the biological processes inwater, the tree resins, in particular colophony and/or colophonyderivatives, are added to the water in an amount of 0.01 mg/l to 10000mg/l, preferably 0.1 mg/l to 1000 mg/l, especially 1 to 100 mg/l.

The tree resins can be applied in the form of saline solutions orsuspensions, preferably as potassium salt solution, especially 0.5 to35% potassium salt solution, or as sodium salt solution, especially 0.5to 35% sodium salt solution. Alternatively, the tree resins can be addedin the form of other 5 to 20% saline solutions or suspensions.

In addition, it is possible to add the tree resins in the form ofalcoholic solution or suspension, preferably as a 1 to 25%, especially10 to 80% ethanol solution.

Advantageously, the tree resins, or their saline or alcoholic solutionsor suspensions, as the case may be, are stabilized prior to their beingadded to the water. For this purpose, they can be mixed with at leastone stabilizing agent, especially with a surface-active agent. Such astabilization hinders or prevents a precipitation or flocculation of thetree resins before they are added to the water. In addition, thestabilizing agents promote the dispersion of the active components assoon as these are added to the water. The stabilization is especiallyadvantageous in the case of a lengthy storage of large amounts of treeresins or colophony and/or colophony derivatives, so that the capacityto control the biological processes in water is always ensured.

The stabilizing agents can be selected from the group comprising dioctylsodium sulfosuccinate, sodium monomethyl naphthalene sulfonate andsodium dimethyl naphthalene sulfonate, N-lauroyl sarcosine sodium salt,alkylpolyglycoside, and sodium dodecyl diphenyl oxide disulfonate.

Further, with particular advantage at least one biocide can be added tothe water in an effective amount. This can be a matter of, for example,a food-compatible, antimicrobial agent (e.g. hops or hop derivatives).To the class of biocides belong also such agents that prevent the growthor genesis of macroorganisms, as for example mussels or the like. Inparticular, the biocide can be selected from a group comprising5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one,glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide,2-bromo-2-nitropropane-1,3-diol, 1-Bromo-1-(bromomethyl)-1,3-propanedicarbonitrile, tetrachloroisophthalonitrile,alkyldimethylbenzylammonium chloride, dimethyldialkylammonium chloride,poly[oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylenedichloride], methylene bisthiocyanate, 2-decylthioethanamine,tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate,cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-1-ethanol,2-(2-bromo-2-nitroethanol)furane, beta-bromo-beta-nitrostyrene,beta-nitrostyrene, beta-nitrovinyl furane,2-Bromo-2-bromomethylglutaronitrile, bis (trichloromethyl) sulfone,S-(2-hydroxypropyl)thiomethane sulfonate,tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione,2-(thiocyanomethylthio)benzothiazole, 2-Bromo-4′-hydroxyacetophenone,1,4-Bis(bromoacetoxy)-2-buten, bis(tributyltin) oxide, copper sulfate,(2-tert-butylamino)-4-chloro-6-ethylamino-s-triazine, dodecylguanidineacetate, dodecylguanidine hydrochloride, coconut alkyldimethylamineoxide, n-coconut alkyltrimethylendiamine, tetraalkyl phosphoniumchloride, 7-Oxabicyclo(2.2.1)heptane-2,3-dicarboxylic acid,2-(4-thiazolyl)benzimidazole, orthophenylphenol,6-ethoxy-1,2,-dihydro-2,2,4-trimethylquinoline, and4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

In order to ensure an effective action of the biocide, the latter can beadded to the water in an amount of 0.01 to 10000 mg/l, preferably 0.05to 50 mg/l, especially 0.1 to 10 mg/l.

In this context, it is equally possible to add a combination of treeresins (especially colophony and/or colophony derivatives) and biocideto the water, or to introduce both components, tree resins and biocide,separately to the water.

According to requirement, the portion of the tree resins can amount to0.1% to 99%, and in an inverted manner the portion of biocide canlikewise amount to 0.1% to 99%.

As already explained above, a certain amount of stabilized tree resinscan be added to the water for control of biological processes. Thisfeature once again follows separately from the independent claim 12.Here, the above-described optional features can be additionallyrealized.

The tree resins or the stabilized tree resins can be added to the waterin dry or paste-like or viscous form. The state of aggregation here canbe dependent on the stabilizing agent or the saline or alcoholicsolutions or suspensions, and can thus be deliberately influencedthrough these.

The tree resins or stabilized tree resins can appropriately be added tothe water at a temperature of −5° C. to 95° C. That is to say, withinthis temperature range it is possible that organisms can grow if nocontrol of the biological processes takes place.

With a further advantage, the tree resins or stabilized tree resins canbe applied in combination with hops or hop derivatives, which arecharacterized through their antimicrobial property.

Advantageously, hop acid can be added to the water, especial beta acid.A mixture of resin acids, especially tree-resin acids, and beta acids,which in particular are added to the water in a 50:50 ratio, leads to anoptimization of the control of biological processes, especially theinhibition of the growth, and the destruction as well as removal ofmicro- and/or macroorganisms.

The following example is intended to make clear the prevention of algaegrowth through the use of resin acids, especially tree-resin acids, e.g.colophony acids, and the synergistic effect with beta acids.

First, a pure culture of Chlorella vulgaris fo. viridis was obtainedfrom CCAP (culture collection of algae and protozoa). This culture wasthen further grown in a fresh and sterile proteose medium. In each case,20 ml of this substance was filled into glass test tubes and differentconcentrations of resin acids and/or beta acids were added. After ninedays, the chlorophyll pigments were extracted and measured. In thefollowing, when resin acids are mentioned, these are in particulartree-resin acids, advantageously colophony acids.

The data analysis was carried out using Jeffrey's and Humphrey'strichromatic equations. The chlorophyll content of a sample afterextraction was determined as 750, 664, 647, and 630 nm through themeasurement of OD. The value of 750 nm was subtracted from theabsorption values of 644, 647, and 630 nm. The concentrations (mg/l) inthe extracted solution of chlorophyll a, b and c₁+c₂ were calculatedthrough use of the 750 nm-corrected absorption values in the followingequations:C _(E,a)=11.85 (Abs 664)−1.54 (Abs 647)−0.08 (Abs 630)C _(E,b)=21.03 (Abs 647)−5.43 (Abs 664)−2.66 (Abs 630)C _(E,c)=24.52 (Abs 630)−7.6 (Abs 647)−1.67 (Abs 664)Where:

-   -   C_(E,a)=the concentration (mg/l) of chlorophyll a that was        analyzed in the extracted solution    -   C_(E,b)=the concentration (mg/l) of chlorophyll b that was        analyzed in the extracted solution    -   C_(E,c)=the concentration (mg/l) of chlorophyll c₁+c₂ that was        analyzed in the extracted solution        Results:

Table 1 shows the amount and type of chlorophyll contained in thecultures of Chlorella vulgaris after their treatment with differentconcentrations of resin and beta acids after an incubation time of ninedays. The results show that 1000 ppm of the resin acids significantlyreduced the chlorophyll portion of a sample, which is a clear indicationof algae-inhibiting activity.

A mixture of 50 ppm resin acids and 50 ppm beta acids reduced thechlorophyll portion of a sample more than in the case of a separateintroduction in each case of 100 ppm of each of the biocides. This showsthe synergistic action between the two components resin acid and betaacid. TABLE 1 Concentration of chlorophyll in the samples after anConcentration incubation time of 9 days [mg/l] of biocides Chlorophyllc₁ + [ppm] Chlorophyll a Chlorophyll b c₂ Control solution 10.12 4.433.42 (without addition)  100 ppm resin acid 11.31 4.6 3.4 1000 ppm resinacid 2 1.25 1.26  100 ppm beta acid 9.3 3.83 2.76 1000 ppm beta acid3.34 1.8 1.47  50 ppm resin 7.04 2.83 1.8 acid + 50 ppm beta acid

The following example shows the prevention of gram-positive bacteriathrough the use of resin acids:

Two strains of the bacteria species Bacillus stearothermophilus, DSM 22and DSM 457, a gram-positive bacteria species, were grown at 55° C. on aculture medium that contained known concentrations of resin acids. Thepercentage growth of the bacteria was measured in comparison to acontrol substance without any resin acids.

The results show that the concentrations of resin acids in a range of 1to 5 ppm have a significant influence on the prevention/retardation ofthe growth of the two bacteria strains.

The following table shows the results of this test: Percentage growth ofbacteria Concentration in comparison to the control of the solution [%]resin acids [ppm] DSM 22 DSM 457 0 ppm 100 100 (Control Solution) 1 ppm90.1 6.4 2 ppm 61.6 5.1 3 ppm 56.2 3.9 4 ppm 0 1.3 5 ppm 0 0

Arising from the independent patent claim 23 is the advantageous use oftree resins in the controlling of biological processes in water,particularly digestion processes in standing or flowing water systems.

An advantageous compound for controlling biological processes in wateris described in the independent patent claims 24 and 27. According topatent claim 24, the compound contains a certain amount of tree resins.Colophony and/or colophony derivatives can be provided as the treeresins. Possible additional features of the compound result from theabove-described method.

According to patent claim 27, the compound contains a certain amount ofstabilized tree resins. With respect to the optional features, referenceis likewise made to the above-described method.

1. Method for controlling digestion processes in water, particularly instanding or flowing water systems, wherein a certain amount of colophonyis added to the water.
 2. Method according to claim 1, wherein inaddition to colophony, colophony derivatives are also applied.
 3. Methodaccording to one of the claims 1, wherein the colophony and/or thecolophony derivatives are added to the water in an amount of 0.01 to10000 mg/l, preferably 0.1 to 1000 mg/l, especially 1 to 100 mg/l. 4.Method according to claim 1, wherein the colophony and/or the colophonyderivatives are applied in the form of saline solutions or suspensions,preferably as potassium salt solution, especially 0.5 to 35% potassiumsalt solution, or as sodium salt solution, especially 0.5 to 35% sodiumsalt solution.
 5. Method according to claim 1, wherein the colophonyand/or the colophony derivatives are added in the form of 5 to 20%saline solutions or suspensions.
 6. Method according to claim 1, whereinthe colophony and/or the colophony derivatives are added in the form ofalcoholic solution or suspension, preferably a 1 to 95%, especially 10to 80% ethanol solution.
 7. Method according to claim 1, wherein thecolophony and/or the colophony derivatives or, as the case may be, theirsaline or alcoholic solutions or suspensions, are mixed with at leastone stabilizing agent, especially a surface-active agent, prior to theiraddition to the water.
 8. Method according to claim 7, wherein thestabilizing agent is selected from the group comprising dioctyl sodiumsulfosuccinate, sodium monomethyl naphthalene sulfonate and sodiumdimethyl naphthalene sulfonate, N-lauroyl sarcosine sodium salt,alkylpolyglycoside, and sodium dodecyl diphenyl oxide disulfonate. 9.Method according to claim 1, wherein at least one biocide is added ineffective amount to the water.
 10. Method according to claim 9, whereinthe biocide is selected from the group comprising5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one,glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide,2-bromo-2-nitropropane-1,3-diol, 1-Bromo-1-(bromomethyl)-1,3-propanedicarbonitrile, tetrachloroisophthalonitrile,alkyldimethylbenzylammonium chloride, dimethyldialkylammonium chloride,poly[oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylenedichloride], methylene bisthiocyanate, 2-decylthioethanamine,tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate,cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-l-ethanol,2-(2-bromo-2-nitroethanol) furane, beta-bromo-beta-nitrostyrene,beta-nitrostyrene, beta-nitrovinyl furane,2-Bromo-2-bromomethylglutaronitrile, bis (trichloromethyl) sulfone,S-(2-hydroxypropyl)thiomethane sulfonate,tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione,2-(thiocyanomethylthio)benzothiazole, 2-Bromo-4′-hydroxyacetophenone,1,4-Bis(bromoacetoxy)-2-buten, bis(tributyltin) oxide, copper sulfate,(2-tert-butylamino)-4-chloro-6-ethylamino-s-triazine, dodecylguanidineacetate, dodecylguanidine hydrochloride, coconut alkyldimethylamineoxide, n-coconut alkyltrimethylendiamine, tetraalkyl phosphoniumchloride, 7-Oxabicyclo(2.2.1 )heptane-2,3-dicarboxylic acid,2-(4-thiazolyl)benzimidazole, orthophenylphenol,6-ethoxy-1,2,-dihydro-2,2,4-trimethylquinoline, and4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
 11. Method according toclaim 9, wherein the biocide is added to the water in an amount of 0.01to 10000 mg/l, preferably 0.05 to 50 mg/l, especially 0.1 to 10 mg/l.12. Method for controlling digestion processes in water, particularly instanding or flowing water systems, wherein a certain amount ofstabilized colophony is added to the water for the enhancement of itschemical stability.
 13. Method according to claim 12, wherein, inaddition, stabilized colophony derivatives are added for the enhancementof their chemical stability.
 14. Method according to claim 13, whereinthe colophony and/or the colophony derivatives are stabilized by meansof at least one surface-active agent.
 15. Method according to claim 1,wherein the stabilizing agent is selected from the group comprisingdioctyl sodium sulfosuccinate, sodium monomethyl naphthalene sulfonateand sodium dimethyl naphthalene sulfonate, N-lauroyl sarcosine sodiumsalt, alkylpolyglycoside, and sodium dodecyl diphenyl oxide disulfonate.16. Method according to claim 12, wherein the stabilized colophonyand/or the stabilized colophony derivatives are added to the water in anamount of 0.01 to 10000 mg/l, preferably 0.1 to 1000 mg/l, especially 1to 100 mg/l.
 17. Method according to claim 12, wherein at least onebiocide is added in effective amount to the water.
 18. Method accordingto claim 17, wherein the biocide is selected from the group comprising5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one,glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide,2-bromo-2-nitropropane-1,3-diol, 1-Bromo-1-(bromomethyl)-1,3-propanedicarbonitrile, tetrachloroisophthalonitrile,alkyldimethylbenzylammonium chloride, dimethyldialkylammonium chloride,poly[oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylenedichloride], methylene bisthiocyanate, 2-decylthioethanamine,tetrakishydroxymethyl phosphonium sulfate, dithiocarbamate,cyanodithioimidocarbonate, 2-methyl-5-nitroimidazole-l-ethanol,2-(2-bromo-2-nitroethanol) furane, beta-bromo-beta-nitrostyrene,beta-nitrostyrene, beta-nitrovinyl furane,2-Bromo-2-bromomethylglutaronitrile, bis (trichloromethyl) sulfone,S-(2-hydroxypropyl)thiomethane sulfonate,tetrahydro-3,5-dimethyl-2H-1,3,5-hydrazine-2-thione,2-(thiocyanomethylthio)benzothiazole, 2-Bromo-4′-hydroxyacetophenone,1,4-Bis(bromoacetoxy)-2-buten, bis(tributyltin) oxide, copper sulfate,(2-tert-butylamino)-4-chloro-6-ethylamino-s-triazine, dodecylguanidineacetate, dodecylguanidine hydrochloride, coconut alkyldimethylamineoxide, n-coconut alkyltrimethylendiamine, tetraalkyl phosphoniumchloride, 7-Oxabicyclo(2.2. 1)heptane-2,3-dicarboxylic acid,2-(4-thiazolyl)benzimidazole, orthophenylphenol,6-ethoxy-1,2,-dihydro-2,2,4-trimethylquinoline, and4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
 19. Method according toclaim 14, wherein the biocide is added to the water in an amount of 0.01to 10000 mg/l, preferably 0.05 to 50 mg/l, especially 0.1 to 10 mg/l.20. Method for controlling digestion processes in water, particularly instanding or flowing water systems, wherein a certain amount ofstabilized colophony is added to the water for the enhancement of itschemical stability, and wherein at least one of the features of claim 4is realized for the stabilized colophony or the stabilized colophonyderivatives.
 21. Method according to claim 1, wherein colophony and/orthe colophony derivatives and/or the stabilized colophony and/or thestabilized colophony derivatives are added in dry or paste-like orviscous form.
 22. Method according to claim 1, wherein the colophonyand/or the colophony derivatives and/or the stabilized colophony and/orthe stabilized colophony derivatives are added to the water at atemperature of −5° C. to 95° C.
 23. Method according to claim 1, whereinthe colophony and/or the colophony derivatives and/or the stabilizedcolophony and/or the stabilized colophony derivatives are applied incombination with hops or hop derivatives.
 24. Application of colophonyin the control of digestion processes in standing or flowing watersystems.
 25. Application according to claim 24, wherein, in addition,colophony derivatives are applied.
 26. Compound for controllingdigestion processes in standing or flowing water systems, wherein thecompound contains a certain amount of colophony.
 27. Compound accordingto claim 26, wherein in addition to colophony, colophony derivatives arealso provided.
 28. Compound for controlling digestion processes instanding or flowing water systems, wherein the compound contains acertain amount of colophony, and wherein at least one of the features ofclaim 3 is realized.
 29. Compound for controlling digestion processes instanding or flowing water systems, wherein the compound contains acertain amount of stabilized colophony for the enhancement of itschemical stability.
 30. Compound according to claim 29, wherein thecompound contains a certain amount of stabilized colophony for theenhancement of its chemical stability.
 31. Compound for controllingdigestion processes in standing or flowing water systems, wherein thecompound contains a certain amount of stabilized colophony for theenhancement of its chemical stability, and wherein at least one of thefeatures of claim 3 is realized.